U.S. patent number 5,710,197 [Application Number 08/501,927] was granted by the patent office on 1998-01-20 for crosslinked polymer particles containing a fluorescent dye.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Andreas Deckers, Wolfgang Fischer, Norbert Guntherberg, Sylke Haremza, Ekkehard Jahns, Werner Ostertag, Helmut Schmidt.
United States Patent |
5,710,197 |
Fischer , et al. |
January 20, 1998 |
**Please see images for:
( Certificate of Correction ) ** |
Crosslinked polymer particles containing a fluorescent dye
Abstract
Fluorescent pigments contain essentially a polymer matrix based
on polymethyl methacrylate and a nonpolar fluorescent dye from the
coumarin or perylene series, the polymer matrix being a crosslinked
polymethacrylate or polyacrylate prepared by suspension
polymerization.
Inventors: |
Fischer; Wolfgang
(Ludwigshafen, DE), Deckers; Andreas (Flomborn,
DE), Guntherberg; Norbert (Speyer, DE),
Jahns; Ekkehard (Hirschberg, DE), Haremza; Sylke
(Neckargemund, DE), Ostertag; Werner (Grunstadt,
DE), Schmidt; Helmut (Osthofen, DE) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
|
Family
ID: |
6523111 |
Appl.
No.: |
08/501,927 |
Filed: |
July 13, 1995 |
Foreign Application Priority Data
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Jul 14, 1994 [DE] |
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44 24 817.2 |
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Current U.S.
Class: |
524/82; 524/92;
546/37; 524/83; 526/204; 524/84; 524/107; 523/351 |
Current CPC
Class: |
C09K
11/06 (20130101); C09K 11/02 (20130101); C08K
5/0041 (20130101); C09D 11/50 (20130101); C09B
67/0061 (20130101); C08K 5/0041 (20130101); C08L
33/10 (20130101) |
Current International
Class: |
C09K
11/02 (20060101); C09B 67/20 (20060101); C08K
5/00 (20060101); C09D 11/00 (20060101); C09B
67/00 (20060101); C08K 005/45 () |
Field of
Search: |
;524/82,83,84,92,107
;546/37 ;526/204 ;523/351 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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422474 |
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Apr 1991 |
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EP |
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277 980 |
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Nov 1991 |
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EP |
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570782 |
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Nov 1993 |
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EP |
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24 51 732 |
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May 1976 |
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DE |
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39 33 093 |
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Apr 1991 |
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DE |
|
Primary Examiner: Cain; Edward J.
Attorney, Agent or Firm: Keil & Weinkauf
Claims
We claim:
1. A process for the preparation of a fluorescent pigment
comprising a polymer matrix based on polymethyl methacrylate and a
nonpolar fluorescent dye from the coumarin or perylene series,
wherein the polymer matrix is a crosslinked polymethacrylate or
polyacrylate prepared by suspension polymerization, wherein a
mixture comprising (A) from 69.9 to 99.8% by weight of a C.sub.8
-C.sub.8 -alkyl ester of acrylic or methacrylic acid,
(B) from 0 to 29.9% by weight of a copolymerizable,
monoethylenically unsaturated monomer and
(C) from 0.1 to 30.0% by weight of a copolymerizable,
polyfunctional, crosslinking monomer is polymerized in suspension
in the presence of
(D) from 0.1 to 15.0% by weight, based on the sum of (A) and (B),
of a nonpolar fluorescent dye from the coumarin or perylene series
and recovering the fluorescent pigment from the reaction
mixture.
2. A process as defined in claim 1, wherein the obtained
fluorescent pigment is recovered in the form of particles having a
diameter of from about 1 to 100 .mu.m.
3. A process as defined in claim 1, wherein the obtained
fluorescent pigment is recovered by filtration.
4. A process as defined in claim 1, wherein the obtained
fluorescent pigment is spray dried.
Description
The present invention relates to fluorescent pigments containing
essentially a poller matrix based on polyethyl methacrylate and a
nonpolar fluorescent dye from the coumarin or perylene series,
wherein the poller matrix is a crosslinked polyethacrylate or
polyacrylate prepared by suspension polymerization.
The present invention furthermore relates to a process for the
preparation of the novel fluorescent pigments, their use for the
production of moldings, films, printing inks, dispersions and
printed products, and moldings, films, printing inks, dispersions
and printing products produced therefrom.
DE-A 39 33 903 describes fluorescent pigments obtainable by mixing
a polymer matrix based on, inter alia, polymethyl methacrylate
containing at least one fluorescent dye from the coumarin or
perylene series. The fluorescent pigments of DE-A 39 33 903 have
very good light fastness, but even better migration fastness is
required for some applications.
It is an object of the present invention to provide further
fluorescent pigments which have both very good light fastness and
very good migration fastness.
We have found that this object is achieved by the fluorescent
pigments defined at the outset.
We have also found a process for the preparation of the novel
fluorescent pigments, their use for the production of moldings,
films, printing inks, dispersions and printed products, and
moldings, films, printing inks, dispersions and printed products
produced therefrom.
The novel fluorescent pigments contain essentially a polymer matrix
and a fluorescent dye from the coumarin or perylene series, the
polymer matrix being a crosslinked polymethacrylate or polyacrylate
prepared in the presence of a fluorescent dye by suspension
polymerization.
The novel fluorescent pigments are preferably obtained by
suspension polymerization of a mixture consisting essentially
of
(A) from 69.9 to 99.8, preferably from 80 to 99.7% by weight of a
C.sub.1 -C.sub.8 -alkyl ester of acrylic or methacrylic acid,
(B) from 0 to 29.9, preferably from 0.1 to 29.9, particularly
preferably from 0.1 to 20, % by weight of a copolymerizable,
monoethylenically unsaturated monomer,
(C) from 0.1 to 30.0, preferably from 0.1 to 20.0, % by weight of a
copolymerizable, polyfunctional, crosslinking monomer and
(D) from 0.1 to 15.0, preferably from 0.1 to 10.0, particularly
preferably from 0.5 to 10.0, % by weight, based on the sum of (A)
and (B), of a nonpolar fluorescent dye from the coumarin or
perylene series.
According to the invention, methyl methacrylate (MMA), ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, sec-butyl
methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl
methacrylate, heptyl methacrylate, octyl methacrylate or
2-ethylhexyl methacrylate, particularly preferably methyl
methacrylate, and mixtures of these monomers, methyl acrylate (MA),
ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl
acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate,
hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethyl-hexyl
acrylate, particularly preferably n-butyl acrylate, and mixtures of
these monomers with one another and with the methacrylates are used
as C.sub.1 -C.sub.8 -alkyl esters of methacrylic or acrylic acid
(component (A)).
Methacrylic acid, acrylic acid, C.sub.1 -C.sub.8 -hydroxyalkyl
esters of methacrylic or acrylic acid, such as 2-hydroxyethyl
acrylate, acrylonitrile, 2-hydroxypropyl methacrylate,
2-hydroxypropyl acrylate, dimethylaminoethyl methacrylate,
dimethylaminoethyl acrylate or styrene, preferably 2-hydroxyethyl
acrylate, acrylic acid and methacrylic acid, or mixtures of the
abovementioned monomers (B), may be used as copolymerizable,
monoethylenically unsaturated monomers (B).
The copolymerizable, polyfunctional, crosslinking monomers (C) used
are in general crosslinking agents which are known per se and which
contain two, three or four, preferably two, double bonds which are
capable of undergoing copolymerization and are not conjugated in
the 1,3 position. Such monomers suitable for crosslinking are, for
example, esters prepared from polyhydride alcohols and methacrylic
or acrylic acid, such as ethylene glycol dimethacrylate, ethylene
glycol diacrylate, butanediol dimethacrylate or butanediol
diacrylate, or allyl compounds, such as allyl methacrylate,
triallyl cyanurate, divinylbenzene, diallyl maleate, diallyl
fumarate or diallyl phthalate, hexanediol dimethacrylate,
hexanediol diacrylate and the acrylate of tricyclodecenyl alcohol,
preferably butanediol diacrylate, hexanediol diacrylate, ethylene
glycol diacrylate and the acrylate of tricyclodecenyl alcohol.
According to the invention, the nonpolar fluorescent dyes (D) used
are those from the coumarin or perylene series.
Suitable nonpolar coumarin dyes are, for example, dyes of this type
as described in U.S. Pat. No. 3,880,869. Coumarin dyes of the
formula I ##STR1## where R.sup.1 and R.sup.2 are identical or
different and, independently of one another, are each C.sub.1
-C.sub.4 -alkyl, in particular ethyl, are noteworthy.
Fluorescent pigments which contain coumarin dyes of the formula II
##STR2## where R.sup.3 is C.sub.1 -C.sub.11 -alkyl, are also
noteworthy.
Suitable nonpolar perylene dyes are, for example, dyes of this type
as described in U.S. Pat. No. 4,618 694, DE-A-2 451 782, U.S. Pat.
No. 379 934, U.S. Pat. No. 4,446,324 or EP-A-277 980.
Other suitable nonpolar perylene dyes are, for example, dyes of
this type as described in EP-A-73 007.
Fluorescent pigments which contain perylene dyes of the formula III
##STR3## where R.sup.4 is C.sub.1 -C.sub.13 -alkyl, are
noteworthy.
Fluorescent pigments which contain perylene dyes of the formula IV
##STR4## where R.sup.5 is hydrogen or cyano and
R.sup.6 is C.sub.1 -C.sub.11 -alkyl,
are particularly preferred.
Fluorescent pigments which contain perylene dyes of the formula V
##STR5## where R.sup.7 is C.sub.5 -C.sub.20 -alkyl which may
contain an oxygen atom in the carbon chain, or is phenyl which is
monosubstituted or polysubstituted by C.sub.1 -C.sub.13 -alkyl or
by C.sub.1 -C.sub.13 -alkoxy, and
R.sup.8 is hydrogen, chlorine or phenoxy which is unsubstituted or
substituted by halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1
-C.sub.14 -alkoxy,
are also particularly preferred.
Fluorescent pigments which contain dyes of the formula V, where
R.sup.7 is phenyl which is monosubstituted or polysubstituted by
C.sub.1 -C.sub.4 -alkyl or by C.sub.1 -C.sub.4 -alkoxy and R.sup.8
is hydrogen, phenoxy or chlorine,
are particularly preferred.
Fluorescent pigments which contain a dye of the formula IV, where
each radical R.sup.5 is cyano and each radical R.sup.6 is butyl,
are very particularly noteworthy.
Fluorescent pigments which contain a dye of the formula V, where
R.sup.7 is 2,6-diisopropylphenyl and R.sup.8 is phenoxy, are also
very particularly noteworthy.
Suitable radicals R.sup.6, R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl
and sec-butyl.
R.sup.6, R.sup.3 and R.sup.4 as well as R.sup.7 are furthermore,
for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl,
2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl,
isooctyl, nonyl, isononyl, decyl, isodecyl or undecyl.
R.sup.7 and R.sup.4 are furthermore, for example, dodecyl, tridecyl
or isotridecyl.
Radicals R.sup.7 are furthermore, for example, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl
(the above names isooctyl, isononyl, isodecyl and isotridecyl are
trivial names and originate from the alcohols obtained by the oxo
synthesis, cf. Ullmanns Enzyklopadie der technischen Chemie, 4th
Edition, Volume 7, pages 215 to 217, and Volume 11, pages 435 and
436), 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or
3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2-or
or 3-isopropoxypropyl, 2- or 3-butoxypropyl, 2- or 3-(2-ethyl
hexyloxy)propyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or
4-propoxybutyl, 2- or 4-isopropoxybutyl, 2- or 4-butoxybutyl, 2- or
4-(2-ethylhexyloxy)butyl, 2-methyl-6-isopropylphenyl,
2-methyl-6-sec-butylphenyl. 2-methyl-6-tert-butylphenyl, 2-ethyl
-6-isopropylphenyl, 2-ethyl-6-sec-butylphenyl, 2-ethyl
-6-tert-butylphenyl, 2-methylphenyl, 2,3-, 2,4-, 2,5- or
2,6-dimethylphenyl, 2,4,6-trimethylphenyl,
2-methyl-4-methoxyphenyl, 2,5-dimethyl-methoxyphenyl,
methoxyphenyl, 2-ethylphenyl, 2,6-diethylphenyl,
2,6-diethyl-4-methylphenyl, 2-isopropylphenyl, 2,4-, 2,5- or
2,6-diisopropylphenyl, 2-n-butylphenyl, 2-sec-butylphenyl,
2-n-pentylphenyl, 2-n-hexylphenyl, 2,5-dimethoxyphenyl,
2,5-diethoxyphenyl, 2,4-dimethoxyphenyl, 2-(2'-methylpentyl)phenyl,
2-n-octylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl,
2,4-diethoxyphenyl, 2,3-dimethoxyphenyl or 2,3-diethoxyphenyl.
Radicals R.sup.8 are, for example, 2-, 3- or 4-fluorophenoxy, 2-,
3- or 4-chlorophenoxy, 2-, 3- or 4-bromophenoxy, 2-, 3- or
4-tert-butylphenoxy, 2-isopropyl-4-methylphenoxy, 2,3-, 2,4-, 2,5-
or 2,6-dichlorophenoxy, 2,4,5- or 2,4,6-trichlorophenoxy, 2-, 3- or
4-methylphenoxy, 2,3-, 2,4-, 2,5-, 2,6- or 3,5-dimethylphenoxy,
2,5,6-trimethylphenoxy, 2-methyl-4-chlorophenoxy,
2-methyl-5-chlorophenoxy, 2-methyl-6-chlorophenoxy, 2-ethylphenoxy,
2,6-diethylphenoxy, 2,6-diethyl-4-methylphenoxy,
2-isopropylphenoxy, 3-methyl-4-chlorophenyl, 4-propylphenoxy,
4-butylphenoxy, 2-, 3- or 4-methoxyphenoxy, 2-, 3- or
4-ethoxyphenoxy, 2-, 3- or 4-propoxyphenoxy, 2-, 3- or
4-isopropoxyphenoxy, 2-, 3- or 4-butoxyphenoxy or
2,4-dimethoxyphenoxy.
The polymerization is carried out in a manner known per se, by the
suspension polymerization method (cf. Houben-Weyl, Methoden der
organischen Chemie, 4th Edition, Vol. XIV/1, Georg Thieme Verlag,
Stuttgart 1961, pages 406-429). For this purpose, the aqueous phase
and monomer phase, containing the components (A), if desired (B),
(C) and (D), are usually initially taken, and conventional
dispersants are added. Water-soluble substances or substances
rendered soluble in water, such as pectins, gelatine,
methylcellulose or other cellulose ethers, are suitable for this
purpose. Polyvinyl alcohol, alkali metal salts of polyacrylic acid
or polymethacrylic acid or alkali metal salts of copolymers of
methyl methacrylate and methacrylic acid may also be used. In
addition, the aqueous phase may be buffered; salts of phosphoric
acid, for example mixtures of sodium dihydrogen phosphate and
disodium hydrogen phosphate, are usual for the alkaline range.
In order to improve the processing properties, heat stabilizers,
for example sterically hindered phenols, and lubricants, such as
stearic acid, may be added.
In order to regulate the molecular weight of the polymer of which
the shell consists, conventional molecular weight regulators or
polymer chain transfer agents can be used in the polymerization.
These are in general oil-soluble compounds. Suitable compounds of
this type are, for example, mercaptans, such as mercaptoethanol,
mercaptopropanol, mercaptobutanols, n-dodecyl mercaptan,
mercaptosuccinic acid, mercaptopropionic acid, mercaptoglycerol,
mercaptoacetic acid, esters of thioglycolic acid, such as hexyl
thioglycolate, mercapto glycol silanes, such as 3-mercaptopropyl
trimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, ethers,
such as dioxane, tetrahydrofuran, tetrahydrofurfuryl alcohol or
tetrahydrofurfuryl acetate, alcohols, such as isopropanol,
n-butanol and n-decanol, and aromatic hydrocarbons, such as
isopropylbenzene.
The regulators used are preferably esters of thioglycolic acid,
such as ethylhexyl thioglycolate and hexyl thioglycolate, and
dodecyl mercaptan. If regulators are used in the polymerization,
the amounts of regulator are preferably from 0.05 to 1.5% by
weight, based on the total amount of monomers.
The polymerization is carried out as a rule in the presence of free
radical polymerization initiators. All conventional peroxo and azo
compounds in the amounts usually used, for example from 0.1 to 5%
by weight, based on the weight of the monomers, may be employed for
this purpose. Preferred polymerization initiators are those which
are soluble in the oil phase or in the monomers.
Examples of these are tert-butyl peroxyneodecanoate, tert-amyl
peroxypivalate, dilauroyl peroxide, tert-amyl
peroxy-2-ethyl-hexanoate, 2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis (2-methylbutyronitrile), dibenzoyl peroxide, tert-butyl
-2-ethylhexanoate, di-tert-butyl hydroperoxide, 2,5-dimethyl
-2,5-di-(tert-butylperoxy)hexane and cumyl hydroperoxide.
Preferably used free radical initiators are
di-(3,5,5-tri-methylhexanoyl) peroxide,
4,4'-azobisisobutyronitrile, tert-butyl perpivalate and dimethyl
2,2'-azobisisobutyrate.
The polymerization temperature is in general from 20.degree. to
150.degree. C., preferably from 40.degree. to 110.degree. C.
The pressure during the polymerization is chosen as a rule to be
from 50 to 2000, preferably from 60 to 500, kPa.
The pH of the reaction mixture is chosen in general to be from 2 to
12, preferably from 4 to 10.
In a preferred embodiment, the reaction batch is purged several
times with an inert gas, such as nitrogen, and is let down each
time. After purging again with inert gas,. the monomer phase is
first suspended at room temperature in the aqueous phase by
stirring and is then heated to the polymerization temperature.
After a reaction time of from 1 to 20, preferably from 2 to 10,
hours, the polymerization is as a rule complete.
With the use of conventional stirrer types, such as impeller
stirrers, observations to date have shown that polymer particles
having a diameter of from 0.1 to 3 mm are obtained in water.
A microsuspension process in which the particle size can be brought
to a desired dimension is particularly advantageous. In addition,
experience to date has shown that particle shapes which are more
uniform than those achievable by milling coarse particles (cf.
DE-A-39 33 903) are obtained. The polymer particles prepared by the
microsuspension process generally have a particle diameter of from
1 to 100 .mu.m (determined by measuring the Fraunhofer diffraction
using a MALVERN Mastersizer). The polymer particles are generally
produced with the aid of highly shearing stirring units, such as
dispersion stirrers or Ultra-TurraX.RTM. units (from IKA
Labortechnik, Staufen), larger amounts of dispersants than usual
normally bring used for stabilizing the monomer droplets during the
polymerization.
After the polymerization, the product is usually filtered off,
washed with water and then dried. The dried novel fluorescent
pigments have, as a rule, a particle size of from 0.1 to 3 mm,
preferably from 0.5 to 3 mm. If desired, smaller particle sizes can
be obtained, for example, by milling.
In a preferred embodiment, particularly when polymerization is
effected by the microsuspension process, the suspension obtained is
processed by spray-drying or filtration and drying in a manner
known per se.
The novel fluorescent pigments may be added either as a dispersion
or after (spray) drying to printing inks or dispersions, in order
to produce, inter alia, printed products. It is also possible to
mix the novel fluorescent pigments into plastics in order, for
example, to produce colored moldings and films, such as luminous
marks and fluorescent plastic films, for example for covering
greenhouses, for decorative purposes and as advertising or
information media.
Compared with the prior art, the novel fluorescent pigments have
both very good light fastness and very good migration fastness.
EXAMPLES
A. Light fastness
The light fastnesses were determined according to DIN 16525 on
prints and were evaluated with the aid of the blue wool scale (DIN
54003).
B. Migration
The migration of the colored pigments was determined according to
DIN 53775.
Printed films of flexible PVC were covered with a white film of
flexible PVC and stored under load for one week at 50.degree. C.
The migration of the pigments into the white film was
evaluated.
C. Particle size determination
The particle size was determined using a MALVERN Mastersizer 3600
(cf. also Verfahrenstechnik 24 (1990), 36 et seq.). The Fraunhofer
diffraction was measured at a wavelength of 633 nm.
The particle size distribution was determined in a range from 1 to
1000 .mu.m, water being used as the solvent.
EXAMPLE 1
The following mixture was introduced into a reaction vessel having
an impeller stirrer:
82 kg of water
574 g of Accumer.RTM. 1530 (polyacrylic acid, 25% strength by
weight in water; Rohm and Haas; viscosity 135-175 mPa.multidot.s at
25.degree. C.; pH 2.1-3.0)
150 g of Na.sub.2 SO.sub.4
48 kg of methyl methacrylate
240 g of allyl methacrylate
120 g of n-dodecyl mercaptan
27.6 g of tert-butyl peroxy-2-ethylhexanoate
20 g of tert-butyl peroxy-3,5,5-trimethylhexanoate
21.1 g of 2,2-bis(tert-butylperoxy)butane
1 kg of fluorescent dye
The kettle content was purged with nitrogen with thorough stirring
and then heated gradually to 120.degree. C. The subsequent
polymerization was carried out for 1.5 hours at 110.degree. C. The
product was filtered off and washed with water. The dried product
had a particle size of from about 0.5 to 3 mm.
EXAMPLE 2
The following mixture was introduced into a 4 l kettle having a
dispenser stirrer (diameter 5 cm):
730 g of water
4.3 g of Na.sub.2 HPO.sub.4 .multidot.12 H.sub.2 O
1.2 g of NaH.sub.2 PO.sub.4 .multidot.2H.sub.2 O
9 g of a 1.6% strength by weight aqueous solution of a co-polymer
of 65% by weight of methacrylic acid and 35% by weight of methyl
methacrylate (neutralized with NaOH to pH 7); (Rohm GmbH;
Rohagit.RTM. S; 3800-5500 mPa.multidot.s at 25.degree. C.;
neutralized 3% strength by weight aqueous solution)
200 g of a 10% strength by weight solution of polyvinyl alcohol
(Hoechst AG, Mowiol.RTM. 40-88) (degree of hydrolysis 88 mol %,
molecular weight M.sub.w of 127,000) in water
442 g of methyl methacrylate
13.5 g of butanediol diacrylate
0.6 g of dilauroyl peroxide
0.15 g of tert-butyl perneodecanoate
9.1 g of fluorescent dye
The mixture was heated to 65.degree. C. in the course of 40 minutes
while stirring at a speed of 3500 min.sup.-1, heated to 73.degree.
C. in a further 30 minutes and kept at 73.degree. C. for 50 minutes
with continuous stirring. Thereafter, the reacting mixture was
transferred by means of a peristaltic pump into a preheated 4 l
kettle provided with an anchor stirrer (150 min.sup.-1) and was
kept there at 73.degree. C. for a further 2.5 hours. Thereafter,
the mixture was heated to 85.degree. C. in the course of one hour
and then cooled. The dispersion obtained had a solids content of
34.5% by weight and consisted of cross-linked particles having a
diameter of from 2 to 8 .mu.m and colored with fluorescent dye.
EXAMPLE 3
As for Example 2, but with 20.25 g of butanediol diacrylate.
EXAMPLE 4
As for Example 2, but with 27 g of butanediol diacrylate.
The stated pigments (the same dye (for formula see below) was used
in all examples and in the experiment according to the prior art)
were tested for their migration fastness and light fastness.
______________________________________ Migration fastness Light
fastness ______________________________________ Example 1 2- >6
Example 2 2+ >6 Example 3 1 >6 Example 4 1 >6 Comparative
Example*) 3 >6 ______________________________________
*)Preparation as described in DE 39 33 903 (Example 2).
Dye used: (from DE-A 39 33 903, Example 2) which corresponds to
U.S. Pat. No. 5,470,502. ##STR6##
* * * * *